Phthalocyanine compounds

ABSTRACT

A compound of formula (1) and salts thereof, wherein: M is a metal or hydrogen; Pc is phthalocyanine nucleus; R 1 , R 2 , W 1  and W 2  are each independently H or optionally substituted alkyl, aryl or aralkyl; R 3  is an aminoalkyl group; L is a divalent organic linking group; x, y and t are each independently 0.5 to 2.5; and (x+y+t) is from 3 to 4. A process for making the compounds of formula (1). The compounds of formula (1) are useful as colorants for inks which are used in for example ink jet printing of substrates such as paper, plastics, textile materials, metal or glass. ##STR1##

This application is a 371 of PCT/GB 96/02297 filed Sep. 20, 1996.

This invention relates to coloured phthalocyanine compounds, inks, theirpreparation and use. The compounds are particularly useful as thecoloured component of ink jet printing inks.

Ink jet printing is a non-impact printing technique which involvesejecting, thermally or by action of an oscillating piezo crystal,droplets of ink continuously or on demand from a fine nozzle directlyonto a substrate such as paper, plastics, textile, metal or glass. Theink may be aqueous, solvent or hot melt based and must provide sharp,non-feathered images which have good water fastness, light fastness andoptical density, have fast fixation to the substrate and cause noclogging of the nozzle.

According to a first aspect of the present invention there is provided acolorant of the Formula (1) and salts thereof: ##STR2## wherein: M is ametal or hydrogen;

Pc is a phthalocyanine nucleus;

R¹, R², W¹ and W² each independently is H or optionally substitutedalkyl , aryl or aralkyl;

R³ is an aminoalkyl group;

L is a divalent organic linking group;

x, y and t are each independently 0.5 to 2.5; and

(x+y+t) is from 3to 4.

M is preferably copper, nickel, scandium, titanium, vanadium, chromium,manganese, iron, cobalt, zinc, lithium, sodium, potassium, magnesium,calcium, barium, aluminium, silicon, tin, lead or rhodium morepreferably copper, nickel, scandium, titanium, vanadium, chromium,manganese, iron, cobalt or zinc, especially copper or nickel and moreespecially copper. When M is tri- or tetra-valent the valencies above 2may be taken by coordination with halogen atoms or oxygen e.g. VO, AlCl,PbCl₂.

R¹, R², W¹ and W² are preferably H; optionally substituted C₁₋₄ -alkyl,especially C₁₋₄ -alkyl; optionally substituted phenyl; C₇₋₁₁ -aralkyl,especially benzyl. It is particularly preferred that R¹ is H, R² is H orC₁₋₄ -alkyl and W¹ and W² are each independently H or C₁₋₄ -alkyl.

The divalent organic linking group represented by L in Formula (1) ispreferably alkylene, especially C₁₋₆ -alkylene, more especially C₂₋₄-alkylene; aralkylene, preferably C₇₋₁₁ -aralkylene, especiallyphenyl-C₁₋₄ -alkylene; or arylene, preferably arylene having up to tencarbon atoms, especially phenylene; which may be substituted orunsubstituted.

As examples of alkylene and aralkylene groups represented by L, theremay be mentioned:

ethylene

1,2- and 1,3-propylene

2-hydroxy -1,3-propylene

1- and 2-phenyl-1,3-propylene

2-(4'-sulphophenyl)-1,3-propylene

1,4-, 2,3- and 2,4-butylene

2-methyl-1,3-propylene

2-methyl-2,4-pentylene

2,2-dimethyl-1,3-propylene

1-phenylethylene

1-chloro-2,3-propylene

1,6- and 2,5-hexylene

2,3-diphenyl-1,4-butylene

1-(methoxycarbonyl)-1,5-pentylene

1-carboxy-1,5-pentylene

2,7-heptylene

3-methyl-1,6-hexylene

--CH₂ CH₂ OCH₂ CH₂ --

--CH₂ CH₂ SCH₂ CH₂ --

--CH₂ CH₂ SSCH₂ CH₂ -- ##STR3##

As examples of arylene radicals represented by L there may be mentioned1,2-, 1,3- and 1,4-phenylene and 1,4-naphthylene which are optionallysulphonated.

It is particularly preferred that L is an optionally substituted C₂ -C₆-alkylene group, more preferably a group of the Formula --C_(n) H_(2n)-- wherein n is 2 to 6. It is preferred that n is 2 to 4, morepreferably n is 2.

R³ can be a primary, secondary or tertiary aminoalkyl group, preferablya group of the Formula --C_(n) H_(2n) -NR⁴ R⁵ wherein n is ashereinbefore defined and R⁴ and R⁵ each independently is H; optionallysubstituted alkyl, aryl or aralkyl; or R⁴ and R⁵ together with thenitrogen atom to which they are attached form a 5 or 6 membered ringother than a piperazino ring.

Preferably R⁴ and R⁵ each independently is H, optionally substitutedC₁₋₄ -alkyl, phenyl or benzyl, more preferably H or C₁₋₄ -alkyl,especially methyl.

When R⁴ and R⁵ together with the nitrogen to which they are attachedform a 5 or 6 membered ring they preferably form a pyridine, piperidineor morpholine ring, more preferably a morpholine ring.

As examples of group s represented by R³ there may be mentioned:

--CH₂ CH₂ NH₂

--CH₂ CH₂ NHCH₂ CH₃

--CH₂ CH₂ N(CH₃)₂

--CH₂ CH₂ NHCH₂ CH₂ CH₃

--CH₂ CH₂ CH₂ NH₂ ##STR4##

When R¹, R², R³, R⁴, R⁵, W¹, W² or L is optionally substituted, thesubstituent(s) is or are preferably selected from H; alkyl, preferablyC₁₋₄ -alkyl and especially methyl; alkoxy, preferably C₁₋₄ -alkoxy andespecially methoxy; carboxy; sulpho; --OH; amino; --CN; --NO₂ ; andhalo.

It is preferred that x is from 0.8 to 2. Preferred values of y are from1 to 2. Preferred values of t are from 0.8 to 2.

The sum of (x+y+t) is preferably 4.

It is to be understood that colorants of the present invention includenot only compounds of Formula (1) but also mixtures of compounds ofFormula (1) and the salts thereof. Preferred salts are those with analkali metal, particularly Na⁺, Li⁺ or K⁺ or a substituted ammoniumcation.

The substituted ammonium cation may be a quaternary ammonium group ofthe Formula ⁺ NQ₄ in which each Q independently is an organic radical,or two or three Qs together with the nitrogen atom to which they areattached form a heterocyclic ring and all remaining Qs are selected fromC₁₋₄ -alkyl. Preferred organic radicals represented by Q are C₁₋₄ -alkylradicals, especially methyl. Preferred heterocyclic rings formed by NQ₄are 5 or 6 membered heterocyclic rings.

As examples of quaternary ammonium groups of Formula ⁺ NQ₄ there may bementioned N⁺ (CH₃)₄, N⁺ (CH₂ CH₃)₄, N-methyl pyridinium, N,N-dimethylpiperidinium and N,N-dimethyl morpholinium.

Alternatively the substituted ammonium cation may be a group of Formula⁺ NHT₃ wherein each T independently is H or C₁₋₄ -alkyl, or two or threegroups represented by T together with the nitrogen atom to which theyare attached form a 5 or 6 membered ring, especially a pyridine,piperidine or morpholine ring.

As examples of groups of Formula ⁺ NHT₃ there may be mentioned (CH₃)₃ N⁺H, (CH₃)₂ N⁺ H₂, H₂ N⁺ (CH₃)(CH₂ CH₃), CH₃ N⁺ H₃, CH₃ CH₂ N⁺ H₃, H₂ N⁺(CH₂ CH₃)₂, CH₃ CH₂ CH₂ N⁺ H₃,⁺ NH₄, (CH₃)₂ CHN⁺ H₃, pyridinium,piperidinium and morpholinium.

According to a further aspect of the present invention there is provideda process for the preparation of a colorant of Formula (1) whichcomprises condensing a compound of the Formula (2) with a compound ofthe Formula (3), preferably in the presence of a base: ##STR5## wherein:B is a labile atom or a labile group; and

M, Pc, R¹, L, R², R³, W¹, W², x, y and t are as hereinbefore defined.

Preferred labile atoms represented by B are halogens, especially Cl andBr, and a preferred labile group represented by B is OSO₃ H.

The base may be any inorganic or organic base such as an alkali metal oralkali earth metal hydroxide, carbonate or bicarbonate or an organicbase, for example the compound of Formula (3). Preferred organic basesare tertiary amines such as N-alkylated heterocycles, for exampleN-(C₁₋₄ -alkyl)morpholine, N-(C₁₋₄ -alkyl)piperidine, and N,N-di(C₁₋₄-alkyl)piperidine; tri(C₁₋₄ -alkyl)amines, for example triethylamine;and optionally substituted pyridines, especially unsubstituted pyridine.

The amount of base used may be varied between wide limits but it ispreferred to use less than 40, more preferably less than 10 andespecially from 3 to 5 moles of base for each mole of the compound ofFormula (2).

The condensation is preferably performed using water as solvent. Ambienttemperatures may be employed in conjunction with a reaction time of, forexample, 5-24 hours, or elevated temperatures of from 30° C. to 150° C.,preferably from 50° C. to 100° C. can be used for a shorter period.

After the condensation the product may be isolated by acidifying thereaction mixture, preferably using a mineral acid, especiallyhydrochloric acid. Where the product precipitates as a solid it may beseparated from the mixture by filtration.

If desired unwanted anions may be removed from the product of the aboveprocess by dialysis, reverse osmosis, ultrafiltration or a combinationthereof.

The product of the above process may be converted, where necessary, tothe alkali metals NH₄ ⁺, quaternary ammonium or organic amine salt bythe addition of ammonia, ammonium hydroxide, primary, secondary,tertiary or quaternary amine. When the base used in the condensationprocess is an organic amine an excess may be used so that the sulphogroups in the compound of Formula (1) are converted into their organicamine salt in situ.

The compounds of Formula (2) may be prepared by stepwise condensation ofa compound of Formula MPc(SO₂ B)_(x+y+t) with a compound of Formula HNR¹-L-B and a compound of Formula HNW¹ W², preferably in an aqueous medium,wherein M, Pc, B, R¹, L, W¹, W², x, y and t are as hereinbefore defined.The condensation leading to the compound of Formula (2) is preferablyperformed in the presence of base.

The abovementioned compound of Formula MPc(SO₂ B)_(x+y+t) may beprepared using known methods, for example by heating a metal-free ormetal-containing phthalocyanine optionally having three to four sulphogroups with chlorosulphonic acid, optionally followed by heating withPCl₃. Typically the heating with chlorosulphonic acid is performed above60° C., preferably above 100° C., especially in the range 120° C. to165° C., preferably over a period of from 1 to 24 hours. Heating withPCl₃ is preferably performed at a lower temperature, especially 80-105°C., over a period of 10 to 48, preferably 10 to 30 hours.

As a result of R³ being an aminoalkyl group the compound of Formula (3)contains at least two amino groups. Consequently when the compound ofFormula (3) is an unsymmetrical diamine, e.g. H₂ NCH₂ CH₂ NHCH₃, amixture of compounds results because either end of the unsymmetricaldiamine can react with the compound of Formula (2).

Examples of compounds of Formula (3) which may be used in the aboveprocess include N,N-dimethylaminoethylamine,2-(2-aminoethylamino)ethanol, N-(aminoethyl)morpholine,1,2-diaminoethane, N-(3-aminopropyl)morpholine, N,N-dimethylaminopropylamine, 1,2-diaminopropane, 1,3-diaminopropane andN,N-diethylaminoethylamine.

The product of the above process forms a further feature of the presentinvention.

The compounds of Formula (1) are especially useful for the preparationof inks and accordingly there is provided an ink comprising a compoundof Formula (1) or salt thereof and a medium, especially aqueous inks,used in ink jet printing and particularly thermal ink jet printing. Theinks can be prepared according to known formulations. The compounds havehigh water fastness when printed onto paper, even when in the form of asalt with a metal (e.g. Na, K). Thus it is preferred to use the freeacid or metal salts of the compounds of Formula (1) rather than thepotentially unpleasant odorous amine salts to achieve good fastnessresults.

A preferred ink comprises a compound of Formula (1) and a liquid medium,preferably an aqueous medium. It is preferred that the colorant iscompletely dissolved in the liquid medium to form a solution.

The ink preferably contains from 0.5% to 20%, more preferably from 0.5%to 15%, and especially from 1% to 5%, by weight of the compound ofFormula (1), based on the total weight of the ink. Although the ink maycontain less than 5% by weight of the compound of Formula (1) it isdesirable that the dye has a solubility of around 10% or more to allowthe preparation of concentrates which may be used to prepare more diluteinks and to minimise the chance of precipitation of the compound ofFormula (1) if evaporation of the medium occurs during use.

The liquid medium is preferably water or a mixture comprising water anda water-soluble organic solvent, preferably in a weight ratio from 99:1to 1:99, more preferably from 95:1 to 50:50 and especially from 90:10 to60:40.

The water-soluble organic solvent is preferably a C₁₋₄ -alkanol such asmethanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol or isobutanol; an amide such as dimethylformamide ordimethylacetamide; a ketone or ketone alcohol such as acetone ordiacetone alcohol; an ether such as tetrahydrofuran or dioxane; apolyalkylene glycol such as polyethylene glycol or polypropylene glycol;an alkylene glycol or thioglycol containing a C₂ -C₆ alkylene group suchas ethylene glycol, propylene glycol, butylene glycol or triethyleneglycol; a thiodiglycol, hexylene glycol, or diethylene glycol; a polyolsuch as glycerol or 1,2,6-hexanetriol; a lower alkyl ether of apolyhydric alcohol such as 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol; 2-pyrrolidone orN-methylpyrrolidone; or a mixture containing two or more of theaforementioned water-soluble organic solvents.

Preferred water-soluble organic solvents are selected from2-pyrrolidone, N-methylpyrrolidone, an alkylene glycol or lower alkylether of a polyhydric alcohol such as ethylene glycol, diethyleneglycol, triethylene glycol or 2-methoxy-2-ethoxy-2-ethoxyethanol; and apolyethylene glycol with a molecular weight of up to 500. A preferredspecific solvent mixture is a binary mixture of water and eitherdiethylene glycol, 2-pyrrolidone or N-methylpyrrolidone in a weightratio as mentioned above.

Examples of suitable ink media are given in U.S. Pat. No. 4,963,189,U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 and EP 4,251,50A.

It is preferred that the inks of the present invention further compriseone or more of a penetrant to assist permeation of the dye into a papersubstrate and a buffer such as sodium borate, to stabilise the pH of theink.

A further aspect of the present invention provides a process forprinting a substrate with an ink using an ink jet printer, characterisedin that the ink contains at least one compound of Formula (1) or saltthereof.

A suitable process for the application of an ink as hereinbefore definedcomprises forming the ink into small droplets by ejection from areservoir through a small orifice so that the droplets of ink aredirected at a substrate. This process is commonly referred to as ink jetprinting, and the ink jet printing processes for the present inks arepreferably piezoelectric ink jet printing, and more especially thermalink jet printing. In thermal ink jet printing, programmed pulses of heatare applied to the ink by means of a resistor, adjacent to the orificeduring relative movement between the substrate and the reservoir.

Substrates may be paper, plastics, textiles, metal or glass. Preferredsubstrates are overhead projector slides or cellulosic substrates,especially plain paper, which may have an acid, alkaline or neutralcharacter.

The preferred ink used in the process is as hereinbefore described.

According to a still further aspect of the present invention there isprovided a paper or an overhead project slide printed with a compound ofFormula (1) or salt thereof.

According to a further aspect of the present invention there is provideda process for the coloration of a textile material with any of theabovementioned ink compositions comprising a compound of Formula (1)which comprises the steps:

i) applying to the textile material by ink jet printing the inkcomposition; and

ii) heating the textile material at a temperature from 50° C. to 250° C.to fix the dye on the material.

The process for coloration of a textile material by ink jet printingpreferably comprises a pre-treatment of the textile material with anaqueous pre-treatment composition comprising a water-soluble base, ahydrotropic agent and a thickening agent followed by removing water fromthe pre-treated textile material to give a dry pre-treated textilematerial which is subjected to ink jet printing in step i) above.

The pre-treatment composition preferably comprises a solution of thebase and the hydrotropic agent in water containing the thickening agent.

The base is preferably an inorganic alkaline base, especially a salt ofan alkali metal with a weak acid such as an alkali metal carbonate,bicarbonate or silicate or an alkali metal hydroxide, The amount of basemay be varied within wide limits provided sufficient base is retained onthe textile material after pre-treatment to promote the dyeing of thepre-treated textile material. Where the base is sodium bicarbonate it isconvenient to use a concentration of from 1% to 5% by weight based onthe total weight of the composition.

The hydrotropic agent is present to provide sufficient water to promotethe fixation reaction between the dye and the textile material duringthe heat treatment, in step (d) above, and any suitable hydrotropicagent may be employed. Preferred hydrotropic agents are urea, thioureaand dicyandiamide. The amount of hydrotropic agent depends to someextent on the type of heat treatment. If steam is used for the heattreatment generally less hydrotropic agent is required than if the heattreatment is dry, because the steam provides a humid environment. Theamount of hydrotropic agent required is generally from 2.5% to 50% byweight of the total composition with from 2.5% to 10% being moresuitable for a steam heat treatment and from 20% to 40% being moresuitable for a dry heat treatment.

The thickening agent may be any thickening agent suitable for use in thepreparation of print pastes for the conventional printing of cellulosereactive dyes. Suitable thickening agents include alginates, especiallysodium alginate, xanthan gums, monogalactam thickeners and cellulosicthickeners. The amount of the thickening agent can vary within widelimits depending on the relationship between concentration andviscosity. However, sufficient agent is preferred to give a viscosityfrom 10 to 1000 mPa.s, preferably from 10 to 100 mPa.s, (measured on aBrookfield RVF Viscometer). For an alginate thickener this range can beprovided by using from 10% to 20% by weight based on the total weight ofthe pre-treatment composition.

The remainder of the pre-treatment composition is preferably water, butother ingredients may be added to aid fixation of the dye to the textilematerial or to enhance the clarity of print by inhibiting the diffusion(migration) of dye from coloured areas to non-coloured areas beforefixation.

Examples of fixation enhancing agents are cationic polymers, such as a50% aqueous solution of a dicyanamide/phenol formaldehyde/ammoniumchloride condensate e.g. MATEXIL FC-PN (available from ICI), which havea strong affinity for the textile material and the dye and thus increasethe fixation of the dye on the textile material.

Examples of anti-migration agents are low molecular weight acrylicresins, e.g. polyacrylates, such as poly(acrylic acid) and poly(vinylacrylate).

In the pre-treatment stage of the present process the pre-treatmentcomposition is preferably evenly applied to the textile material. Wherea deeply penetrated print or a deep shade is required the pre-treatmentcomposition is preferably applied by a padding or similar process sothat it is evenly distributed throughout the material. However, whereonly a superficial print is required the pre-treatment composition canbe applied to the surface of the textile material by a printingprocedure, such as screen or roller printing, ink jet printing or barapplication.

In the pre-treatment stage of the present process, water may be removedfrom the pre-treated textile material by any suitable drying proceduresuch as by exposure to hot air or direct heating, e.g. by infra-redradiation, or micro-wave radiation, preferably so that the temperatureof the material does not exceed 100° C.

The application of the ink composition to the textile material, stage(i) of the present process, may be effected by any ink jet printingtechnique, whether drop on demand (DOD) or continuous flow. The inkcomposition, preferably also contains a humectant to inhibit evaporationof water and a preservative to inhibit the growth of fungi, bacteriaand/or algae in the solution. Examples of suitable humectants are,propan-1,2-diol, butan-1,2-diol, butan-2,3-diol and butan-1,3-diol.However, the presence of small amounts, up to about 10%, preferably notmore than 5%, in total, of polyols having two or more primary hydroxyand/or primary alcohols is acceptable, although the composition ispreferably free from such compounds. Where the ink jet printingtechnique involves the charging and electrically-controlled deflectionof drops the composition preferably also contains a conducting materialsuch as an ionised salt to enhance and stabilise the charge applied tothe drops. Suitable salts for this purpose are alkali metal salts ofmineral acids.

After application of the ink composition, it is generally desirable toremove water from the printed textile material at relatively lowtemperatures (<100° C.) prior to the heat applied to fix the dye on thetextile material as this has been found to minimise the diffusion of thedye from printed to non-printed regions. As with the pre-treated textilematerial removal of water is preferably by heat, such as by exposure tohot air or to infrared or micro-wave radiation.

In stage (ii) of the present process, the printed textile material issubmitted to a short heat treatment, preferably after removal of waterby low-temperature drying, at a temperature from 100° C. to 200° C. byexposure to dry or steam heat for a period of up to 20 minutes. If asteam (wet) heat treatment is used, the printed material is preferablymaintained at 100-105° C. for from 5 to 15 minutes whereas if a dry heattreatment is employed the printed material is preferably maintained at140-160° C. for from 2 to 8 minutes.

After allowing the textile material to cool, unfixed dye and otheringredients of the pre-treatment and dye compositions may be removedfrom the textile material by a washing sequence, involving a series ofhot and cold washes in water and aqueous detergent solutions before thetextile material is dried.

According to further aspects of the present invention there are providedtextile materials, especially cellulosic textile materials, colouredwith any of the ink compositions according to the present invention orby means of the process according to the present invention.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 Preparation of a Compound of Formula (5) ##STR6##

C. I. Reactive Blue 25 (CuPc (SO₃ H)₁.3 (SO₂ NHC₂ H₄ Cl)₁.5 (SO₂ NH₂)₁.2from Zeneca Specialties, England (15.0 g)) was dissolved in water (300cm³) by addition of 2N NaOH to give a solution of pH 8.0.N,N-dimethylaminoethylamine (15.0 g) was added and the mixture stirredat 70-80° C. for 4 hours.

The mixture was cooled to 50° C. and the pH adjusted to 6.0 by additionof concentrated hydrochloric acid and the product, in free acid form,was filtered off at 25° C. and washed with water (500 cm³).

The product was added to water (300 cm³) and dissolved by addition of 2Nsodium hydroxide to give a solution of pH 10. The solution was dialysedto remove chloride ions, screened and evaporated to dryness to give thesodium salt of the compound of Formula (5) .

The product was made into an ink by dissolving 2 parts inwater/diethylene glycol (92.5/7.5) and printed onto plain paper using athermal ink jet printer. The product gave bright cyan shades with highwater fastness and good light fastness.

EXAMPLE 2 Preparation of a Compound of Formula (6) ##STR7##

Example 1 was repeated except that in place ofN,N-dimethylaminoethylamine (15 g) there was used N-(3-aminopropyl)morpholine (15 g). The product was converted to the ammonium salt anddialysed, screened evaporated and dried.

When made into an ink by dissolving 2 parts in water/diethylene glycol(92.5/7.5) and printed onto plain paper using a thermal ink jet printerthe title product gave bright cyan prints with high water-fastness andgood light-fastness.

EXAMPLE 3 Preparation of a Compound of Formula (7) ##STR8##

Example 1 was repeated except that in place ofN-N-dimethylaminoethylamine (15 g) there was used3-N,N-dimethylaminopropylamine (15 g). The sodium salt of the colorantwas dialysed, screened, evaporated and dried.

When made into an ink by dissolving 2 g in water/2-pyrrolidone (90/10)and printed on plain paper using a thermal ink jet printer the titleproduct gave bright cyan shades with high water-fastness and goodlight-fastness.

EXAMPLE 4 Preparation of a Compound of Formula (8) ##STR9##

Example 1 was repeated except that in place ofN-N-dimethylaminoethylamine (15 g) there was usedN-(2-hydroxyethyl)ethylene diamine (15 g). The sodium salt of thecolorant was dialysed, screened, evaporated and dried.

When made into an ink by dissolving 2 parts in water/diethylene glycol(92.5/7.5) and printed onto plain paper using a thermal ink jet printerthe title product gave bright cyan prints having high waterfastness andgood light fastness.

EXAMPLE 5

Preparation of a Compound of Formula (9) ##STR10##

Example 1 was repeated except that in place ofN,N-dimethylaminoethylamine (15 g) there was used 1,3-propylene diamine(15 g). The sodium salt of the colorant was dialysed, screened,evaporated and dried.

When made into an ink by dissolving 2 g in water/2-pyrrolidone (90/10)and printed onto plain paper using a thermal ink jet printer the titleproduct gave bright cyan prints having high water-fastness and goodlight-fastness.

EXAMPLE 6 Preparation of a Compound of Formula (10) ##STR11##

Example 1 was repeated except that in place ofN-N-dimethylaminoethylamine (15 g) there was used 1,2-propylene diamine(15 g). The sodium salt of the colorant was dialysed, screened,evaporated and dried as in Example 1.

When made into an ink by dissolving 2 parts in water/2-pyrrolidone(90/10) and printed onto plain paper using a thermal ink jet printer thetitle product gave bright cyan prints having high water-fastness andgood light-fastness.

EXAMPLE 7 Preparation of a Compound of Formula (11) ##STR12##

Example 1 was repeated except that in place ofN,N-dimethylaminoethylamine (15 g), there was usedN-(2-aminoethyl)-morpholine (15 g). The produce was converted to theammonium salt and dialysed, screened, evaporated and dried.

When made into an ink by dissolving 2 parts in water/diethylene glycol(92.5/7.5) and printed onto plain paper using a thermal ink jet printer,the title produce gave bright cyan prints with high water fastness andgood light fastness.

We claim:
 1. A compound of Formula (1) and salts thereof: ##STR13## inwhich: M is selected from the group consisting of a metal andhydrogen;Pc is a phthalocyanine nucleus; R¹, R², W¹ and W² are eachindependently selected from the group consisting of H, optionallysubstituted alkyl, optionally substituted alkyl, optionally substitutedaryl, and optionally substituted aralkyl; R³ is an aminoalkyl group offormula --C_(n) H_(2n) NR⁴ R⁵ ; Where n is from 2 to 6; and R⁴ and R⁵are selected from the group consisting of:a. where R⁴ and R⁵ areindependently selected from a group consisting of: H, optionallysubstituted alkyl, optionally substituted aryl; and optionallysubstituted aralkyl; and b. where R⁴ and R⁵, together with the nitrogenatom to which they are attached, form a ring selected from the groupconsisting of pyridine, piperidine and morpholine; L is selected fromthe group consisting of optionally substituted alkylene; optionallysubstituted aralkylene; and optionally substituted arylene; x, y and tare each independently 0.5 to 2.5; and (x+y+t) is from 3 to 4;where theoptional substituents are selected from the group consisting of H, C₁₋₄alkyl, C₁₋₄ alkoxy, carboxy, sulpho, --OH, amino, --CN, --NO, and halo.2. A compound according to claim 1, in which R⁴ and R⁵ are eachindependently selected from the group consisting of H, optionallysubstituted C₁₋₄ -alkyl, optionally substituted phenyl, and optionallysubstituted benzyl.
 3. A compound according to claim 1, in which L isselected from the group consisting of optionally substituted C₁₋₆alkylene, optionally substituted C₇₋₁₁ aralkylene, and optionallysubstituted arylene having up to ten carbon atoms.
 4. A compoundaccording to claim 1, in which M is copper.
 5. A compound according toclaim 1, in which:x is from 0.8 to 2, y is from 1 to 2 and t is from 0.8to
 2. 6. A compound according to claim 1, in which the sum of (x+y+z) is4.
 7. An ink comprising a compound of Formula (1) or salt thereofaccording to claim 1 and a liquid medium.
 8. An ink according to claim7, in which is liquid medium comprises water and a water-soluble organicsolvent in a weight ratio of 99:1 to 1:99.
 9. A process for printing asubstrate comprising the step of applying to the substrate with an inkjet printer an ink according to claim
 7. 10. A process for thecoloration of textile material with an ink according to claim 11, theprocess comprising:applying the ink to the textile material by ink jetprinting; and heating the textile material at a temperature from 50° C.to 250° C., wherein, said heating the textile material fixes the dye onthe material.
 11. A substrate selected from the group consisting of atextile material, paper, and an overhead projector slide, wherein thesubstrate is printed with an ink according to claim
 7. 12. A process forthe preparation of a colorant of Formula (1) according to claim 1, whichcomprises condensing, preferably in the presence of a base, a compoundof Formula (2); ##STR14## in which: M, Pc, R¹, L, W¹, W², x, y and t areas defined in claim 1 and B is selected from the group consisting ofhalo and --OSO₃ H;with a compound of Formula (3): ##STR15## in which R²and R³ are as defined in claim 1.